PtCl(1,1'-binaphthane-2,2'-diyl 2,4-di-t-Bu-phenyl phosphite)(1,1'-binaphthane-2,2'-diyl 2,4-di-tert-butylphenyl phosphite(-1H)) | 1188508-71-5

• 英文名称: PtCl(1,1'-binaphthane-2,2'-diyl 2,4-di-t-Bu-phenyl phosphite)(1,1'-binaphthane-2,2'-diyl 2,4-di-tert-butylphenyl phosphite(-1H))
• 英文别名: cis-PtCl((κ2-P,C-P(OC6H2-2,4-tBu2)((R)-binolate))((R)-binolate)(2,4-di-tert-butyl)phosphite)
• CAS: 1188508-71-5
• 化学式: C₆₈H₆₅ClO₆P₂Pt
• 分子量: 1270.74
• InChiKey: QZXCBFJNWYNIOK-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为产物：
  描述：

  (R)-1,1'-binaphthane-2,2'-diyl 2,4-di-tert-butylphenyl phosphite 以 二氯甲烷 、 乙二醇甲醚 为溶剂， 生成 PtCl(1,1'-binaphthane-2,2'-diyl 2,4-di-t-Bu-phenyl phosphite)(1,1'-binaphthane-2,2'-diyl 2,4-di-tert-butylphenyl phosphite(-1H))
  参考文献：
  名称：

  手性邻-钯和-铂芳基亚磷酸酯配合物

  摘要：

  一系列手性双-亚磷酸酯络合物的8 - 11 [的MC1 2（L）2 ]（M = Pd或Pt）和邻位-metalated，C，P螯合物键合的单亚磷酸酯配合物12 - 14 [M（κ 2 -L ）（μ-Cl）] 2是通过在适当条件下使对映纯（R）-BINOL衍生的亚磷酸亚芳基酯配体L与易于获得的钯或铂前体反应制得的。复合物的反应活性12 - 14含手性C，P研究了对各种单齿和双齿配体的双齿键合的芳基亚磷酸酯配体。已发现邻位钯配合物12和13在二氯甲烷中不能与三苯基膦干净地反应，而邻位铂配合物14与典型的单齿或双齿配体（如吡啶，三苯基膦，三环己基膦，三苯基亚磷酸酯和[1,2]）平稳反应。双（二苯基膦基）乙烷]，以生成相应的手性单体邻-platinated络合物18 - 23产量高到极好。除了通过NMR技术和质谱以及元素分析，复合物的结构的所有新颖的复合物的全面表征10，18，19，和23在固体状

  DOI：

  10.1021/om9003237

文献信息

• Chiral triaryl phosphite-based palladacycles and platinacycles: synthesis and application to asymmetric Lewis acid catalysis
  作者：Robin B. Bedford、Helena Dumycz、Mairi F. Haddow、Lukasz T. Pilarski、A. Guy Orpen、Paul G. Pringle、Richard L. Wingad

  DOI：10.1039/b907333g

  日期：——

  The optically pure monophosphites P(OAr)(BINOLate) (7, where Ar = 2,4-di-tert-butylphenyl) have been prepared by treatment of PCl2(OAr) with R- or S-BINOL. Treatment of [PdCl2(NCMe)2] with 7 gave [PdCl2(7)2] (9) or the binuclear orthometallated complex [Pd2Cl2(7-H)2] (8) depending on the reaction conditions. Bridge cleavage reactions of 8 gave [PdCl(7-H)(L)] with L trans to carbon when L = PPh3 or 7 and cis to carbon when L = N-heterocyclic carbene. Treatment of [PtCl2(NCtBu)2] with 7 gave [PtCl2(7)2] (18) which upon further reaction with PtCl2 furnished a mixture of binuclear [Pt2Cl2(7-H)2] (17) and cis-[PtCl(7-H)(7)] (19). The palladium complexes containing cyclometallated 7 were screened for catalysis of 1,4-conjugate addition of phenylboronic acid to cyclohexen-2-one and the allylation of benzaldehyde with allyltributyltin. Conversions were generally high in each case but enantioselectivities were low (15% e.e. at best). The X-ray crystal structures of 8, 17 and [PdCl(7-H)(NHC)] (10a, where NHC = 1,3-(dimesityl)imidazolidin-2-ylidene) have been determined.

  通过将PCl2(OAr)与R-或S-BINOL反应，制备了光学纯的单膦酸酯P(OAr)(BINOLate) (7, 其中Ar = 2,4-二叔丁基苯基)。将[PdCl2(NCMe)2]与7反应，根据反应条件得到[PdCl2(7)2] (9)或二核邻金属配合物[Pd2Cl2(7-H)2] (8)。8的桥断裂反应得到当L = PPh3或7时与碳反式排列的[PdCl(7-H)(L)]，当L = N-杂环卡宾时与碳顺式排列。将[PtCl2(NCtBu)2]与7反应得到[PtCl2(7)2] (18)，进一步与PtCl2反应得到二核[Pt2Cl2(7-H)2] (17)和顺式-[PtCl(7-H)(7)] (19)的混合物。含环金属化7的钯配合物被筛选用于催化苯硼酸对环己烯-2-酮的1,4-共轭加成和苯甲醛与三丁基锡烯烃的烯丙基化反应。每种情况下的转化率一般都很高，但对映选择性较低（最好的情况下为15% 对映体过量）。8、17和[PdCl(7-H)(NHC)] (10a, 其中NHC = 1,3-(二甲基)咪唑啉-2-亚基)的X射线晶体结构已经确定。